WO2009144159A1 - Pyridin-4-yl-méthyl sulfonamides substitués en tant que fongicides - Google Patents

Pyridin-4-yl-méthyl sulfonamides substitués en tant que fongicides Download PDF

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WO2009144159A1
WO2009144159A1 PCT/EP2009/056125 EP2009056125W WO2009144159A1 WO 2009144159 A1 WO2009144159 A1 WO 2009144159A1 EP 2009056125 W EP2009056125 W EP 2009056125W WO 2009144159 A1 WO2009144159 A1 WO 2009144159A1
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alkyl
compounds
alkoxy
formula
haloalkyl
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PCT/EP2009/056125
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Alice GLÄTTLI
Wassilios Grammenos
Bernd Müller
Jan Klaas Lohmann
Marianna Vrettou
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Basf Se
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Priority to US12/994,572 priority Critical patent/US20110077154A1/en
Priority to BRPI0912109-9A priority patent/BRPI0912109A2/pt
Priority to JP2011510950A priority patent/JP2011521924A/ja
Priority to EP09753814A priority patent/EP2300471A1/fr
Priority to CN2009801196435A priority patent/CN102046623A/zh
Publication of WO2009144159A1 publication Critical patent/WO2009144159A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/056—Ortho-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to compounds of formula I
  • Het is a fused-on 5- or 6-membered partially unsaturated or aromatic heterocycle wherein the ring member atoms of the fused-on heterocycle include besides carbon atoms 1 , 2 or 3 heteroatoms selected from the group of N, O and S;
  • R f is halogen, CN, NO 2 , Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy,
  • Ci-Cio-haloalkoxy Ci-Cio-alkenyl, Ci-Cio-alkynyl or NR 1 R 2 ;
  • n 0, 1 , 2, 3, 4 or 5, wherein R f radicals are identical or different if m is 2, 3, 4 or 5;
  • R a is halogen, CN, NH 2 , NO 2 , OH, SH, d-Ce-alkyl, Ci-C 6 -haloalkyl, d-Ce-alkoxy, d-Ce-haloalkoxy, d-Ce-alkylthio, d-Ce-haloalkylthio, Ci-Ce-alkylsulfinyl, Ci-C ⁇ -haloalkylsulfinyl, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -haloalkylsulfonyl, Ci-C ⁇ -alkyl- amino, di(Ci-C6-alkyl)amino, C 2 -C6-alkenyl, C 2 -C6-haloalkenyl, C 2 -C6-alkynyl, C 2 -C 6 -haloalkynyl, d-Ce-alkoxy-d-C
  • n 0, 1 or 2, wherein R a radicals are identical or different if n is 2;
  • R is hydrogen, d-Ce-alkyl, d-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -Cy- cloalkyl, Ci-C6-alkyl-C3-C8-cycloalkyl or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1 , 2, 3, 4 or 5 substituents selected from the group consisting of CN, halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy, Ci-C6-halo- alkoxy, Ci-C6-alkoxycarbonyl and di(Ci-C6-alkyl)aminocarbonyl;
  • A is phenylene or a 5- or 6-membered heteroarenediyl, wherein the ring member atoms of the 5-membered heteroarenediyl include besides carbon atoms 1 , 2, 3 or 4 nitrogen atoms or 1 oxygen atom or 1 , 2 or 3 nitrogen atoms and 1 sulfur or oxygen atom, and wherein the ring member atoms of the 6-membered het- eroarenediyl include besides carbon atoms 2 or 3 nitrogen atoms, and wherein the aforementioned divalent radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different groups R b :
  • R b is halogen, CN, NO 2 , d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, Ci-C 6 -halo- alkoxy, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, (Ci-C6-alkyl)carbonyl, (Ci-C6-alkoxy)carbonyl, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, (Ci-C6-alkyl)aminocarbonyl and di(Ci-C6-alkyl)aminocarbonyl; or
  • R b that are bound to adjacent ring member atoms of the group A may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different groups as defined for R b ;
  • R ⁇ is hydrogen or Ci-C6-alkyl
  • R c is halogen, CN, NO 2 , NH 2 , d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, d-Ce-halo- alkoxy, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, d-C ⁇ -alkylthio, Ci-C ⁇ -haloalkyl- thio, Ci-C ⁇ -alkylsulfinyl, Ci-C ⁇ -haloalkylsulfinyl, Ci-C ⁇ -alkylsulfonyl, Ci-C ⁇ -halo- alkylsulfonyl, Ci-Ce-alkoxy-Ci-Ce-alkyl, Ci-Ce-haloalkoxy-Ci-Ce-alkyl, C 2 -C 6 -alk- enyl, C 2 -C 6 -alkynyl,
  • p is 0, 1 , 2, 3, 4 or 5, wherein R c radicals are identical or different if p is 2, 3, 4 or 5;
  • R' is hydrogen, NH 2 , d-Ce-alkyl, d-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl,
  • Ci-C ⁇ -alkoxy Ci-C ⁇ -alkoxy-d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C ⁇ -alkyl- amino or di(Ci-C6-alkyl)amino;
  • R" is hydrogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl or C-i-Ce-alkoxy-C-i-Ce-alkyl, R'" is hydrogen or d-C ⁇ -alkyl;
  • R d is halogen, CN, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or Ci-C ⁇ -haloalkoxy;
  • R c that are bound to adjacent ring member atoms of the phenyl ring may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle, which may be a carbocycle or heterocy- cle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused cycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different radicals R e :
  • R e is halogen, CN, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy or Ci-C ⁇ -haloalkoxy;
  • the invention also relates to processes and intermediates for preparing such com- pounds, to agrochemical compositions comprising a solvent or solid carrier and at least a compound of formula I or an N-oxide or an agriculturally acceptable salt thereof and their use for combating phytopathogenic fungi, and seed comprising a compound of formula I, or an N-oxide or an agriculturally acceptable salt thereof.
  • WO 05/033081 describes pyridin-4-ylmethyl sulfonamides and their use for combating phytopathogenic fungi.
  • WO 06/097489 and WO 08/031824 describe various pyri- din-4-ylmethylamides of biphenyl sulfonic acid and their use as fungicides and insecticides, respectively.
  • WO 07/093599 and WO 08/022937 describe pyridin-4-ylmethyl- amides of pyridiylsulfonic acid and thiophenesulfonic acid, respectively, and their use as fungicides.
  • the compounds according to the present invention differ from those described in WO 05/033081 and WO 06/097489 by having a pyridin-4-ylmethyl group carrying a fused-on heterocycle.
  • a further aspect of the present invention relates to a process for preparing com- pounds I as defined before, which comprises reacting compounds II, wherein Het, R a , R f , m, n, and R are defined as above, under basic conditions with compounds III, wherein R c , p, A and Y are defined as above and L is a nucleophilic leaving group such as halogen, substituted phenoxy, N3, heterocyclyl or heterocyclyloxy, preferably penta- fluorphenoxy, heterocyclyl such as imazolyl, pyrazolyl or triazolyl, or halogen such as chloro, fluoro or bromo, as shown below:
  • This reaction is usually carried out at temperatures of from -30 to 120 0 C, preferably from -10 to 100 0 C, in an inert organic solvent in the presence of a base.
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as dichloromethane (DCM), chloroform and chloro- benzene, ethers, such as diethyl ether, diisopropyl ether, methyl tert.
  • DCM dichloromethane
  • ethers such as diethyl ether, diisopropyl ether, methyl tert.
  • MTBE -butyl ether
  • dioxane dioxane
  • anisole and tetrahydrofuran (THF) nitriles such as acetonitrile and propionitrile
  • ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert- butyl methyl ketone, and also dimethyl sulfoxide (DMSO), dimethyl formamide (DMF) and dimethyl acetamide, preferably THF, MTBE, dichloromethane, chloroform, acetonitrile, toluene or DMF, and also mixtures thereof.
  • DMSO dimethyl sulfoxide
  • DMF dimethyl formamide
  • acetamide preferably THF, MTBE, dichloromethane, chloroform, acetonitrile, toluene or DMF, and also mixtures thereof.
  • Suitable bases are, in general, inorganic compounds such as alkali metal and alka- line earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicar- bonates such as sodium bicarbonate, moreover organic bases, e.g.
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine (NMP), pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylamino- pyridine, and also bicyclic amines.
  • NMP N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylamino- pyridine
  • bicyclic amines Particular preference is given to triethylamine, pyri- dine, triethylamine and potassium carbonate.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the amount of base is typically 0.5 to 5 molar equivalents relative to 1 mole of compounds II.
  • the starting materials i.e. compounds Il and compounds III, are generally reacted with one another in equimolar amounts. In terms of yield it may be advantageous to employ an excess of compound Il based on compound III.
  • compounds IV wherein Het, R a , R f , m and n are as defined above and L' is a leaving group such as methylsulfonyl, toluenesulfonyl, hydroxyl or a group as defined for L in formula III, preferably, methylsulfonyl, toluenesulfonyl or halogen such as chloro, bromo and iodo, can be reacted with compounds III.
  • a wherein R, R c , p, A and Y are as defined above, to obtain directly compounds I as shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds Il with compounds III. Should other leaving groups L' than hydroxy be desired, the hydroxy group can be effectively reacted to form the leaving group in question, e. g. in situ upon treatment with triphenylphosphine and diethylazodicarboxylate or diisopropylazodicarboxylate or a suitable substitute as described in Organ. Lett. 8, 5069-5072, 2006. Alternatively, this reaction may also be carried out in two consecutive steps as shown below, wherein Het, R a , R c , R f , m, n, p, R, A, Y and L are defined as above:
  • R c , R d , m, n, p, R, A, Y and L are defined as above:
  • Some compounds Il are known from the literature (cf. Bioorg. Med. Chem. 15(7), 2759-2767, 2007; US 2007/129547; WO 07/64993), are commercially available or they can be prepared by reactions known in the art e. g. by treatment with ammonia or ammonium acetate in the presence or absence of a suitable iodide salt, such as NaI, Kl or tetrabutylammonium iodide, in an analogous fashion to the one described in WO 07/69685.
  • compounds Il may be prepared starting from derivatives IV by treatment with a suitable phthalimide salt, preferably K + or Na + salt, followed by hydrazine, as illustrated in US 2007/129547.
  • compounds II, wherein R is hydrogen can be prepared by reduction of the corresponding oximes IX.a, nitriles IX.b, or amides IX.c or by reductive amination of the corresponding aldehydes IX. d or ketones IX. e as described below. Appropriate methods therefore are known to those skilled in the art:
  • oximes IX.a can be prepared prepared by reactions known in the art, e. g. from either the respective aldehydes IX.d, ketones IX.e, or the methyl derivatives IX.f in analogy to methods described by Houben-Weyl, vol. 10/4, Thieme, Stuttgart, 1968; vol. 1 1/2, 1957; vol E5, 1985; J. Prakt. Chem./Chem. Ztg.
  • the aldehydes IX.d can be synthesized from the corresponding methyl derivatives IX.f in analogy to J. Org. Chem. 51 (4), 536-537, 1986, or from halogenated derivatives IX.g as shown in Eur. J. Org. Chem. 2003(8), 1576-1588, 2003; Tetrahedron Lett. 40(19), 3719-3722 1999; or Tetrahedron 55(41), 12149-12156, 1999.
  • the ketones IX.e may be prepared by oxidation of the corresponding alcohols using standard agents, e.g. in analogy to the methods described in Synthesis 11 , 881-884; or Heterocycles 71 (4), 91 1-918.
  • nitriles IX.b can be prepared in analogy to methods described in Heterocycles, 41 (4), 675 (1995); Chem. Pharm. Bull., 21 , 1927 et sqq. (1973); or J. Chem. Soc, 426 et sqq. (1942); e.g. from the corresponding halogenated derivatives IX.g by reaction with cyanides such as CuCN, NaCN or KCN or in analogy to the route described in Monatsh. Chem. 87, 526-536, (1956), e.g.
  • halogenated deriva- tives IX.g by reaction with a trialkylamine to afford the trialkylammonium substituted derivatives, followed by reaction with suitable cyanation reagents such as organic or inorganic cyanides, e.g. tetraalkylammonium cyanides, NaCN or KCN.
  • suitable cyanation reagents such as organic or inorganic cyanides, e.g. tetraalkylammonium cyanides, NaCN or KCN.
  • the compounds IX.g are commercially available or can be synthesized according to standard methods.
  • the amides IX. c can be prepared, e.g. from the corresponding carboxylic acid chlo- rides or anhydrides by reaction with ammonia, e.g. as described in March, J. "Advanced Organic Chemistry: Reactions, Mechanisms, and Structure” (Wiley & Sons, New York, 3th edition, 1985, 370-371 ).
  • PG is a suitable protection group that may be cleaved under acidic, basic or standard hydrogenation conditions such as defined below:
  • Protection of amino groups against reaction during one or more synthesis steps is a procedure well known and described in the art.
  • suitable protection groups are those which are customarily used in organic synthesis, preferably t-butyloxy- carbonyl, benzyloxycarbonyl, allyloxy-carbonyl, diformyl or phthaloyl. Further details on suitable protection groups and their cleavage may be found in Greene T. W., Wits P. G. "Protective groups in organic synthesis” (Wiley & Sons, New York, 1999, 494 et sqq.).
  • the hydrogenation of the nitriles IX.b can be advantegously performed in the presence of suitable catalysts, preferably Raney nickel or palladium-on-carbon, and protection reagents such as di-tert. -butyl dicarbonate, dibenzyl dicarbonate, benzyl chloroformate, to yield the N-protected compounds X.
  • suitable catalysts preferably Raney nickel or palladium-on-carbon
  • protection reagents such as di-tert. -butyl dicarbonate, dibenzyl dicarbonate, benzyl chloroformate
  • Compounds IV, wherein L' is halogen, preferably Cl or Br, may be synthesized un- der standard halogenation conditions, e. g. by treatment of the corresponding methyl derivative IX.f with halogenation reagents such as Cb, Br2, N-chlorosuccinimide, N-bromosuccinimide or isocyanuric chloride in analogy to methods described in Bioorg. Med. Chem. 15(10), 3315-3320; 2007, Eur. J. Org. Chem. 4, 947-957, 2006; J. Med. Chem. 48(5), 1367-1383, 2005; or J. Org. Chem. 68(11 ), 4179-4188, 2003.
  • halogenation reagents such as Cb, Br2, N-chlorosuccinimide, N-bromosuccinimide or isocyanuric chloride
  • reaction is carried out at temperatures of from 0 0 C to 200 0 C, pref- erably from 25°C to 200 0 C, in an inert organic solvent in the presence of a strong Br ⁇ nsted or Lewis acid.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, haloge- nated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as di- ethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as aceto- nitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, N-ethyl-2-pyrrolidone (NEP) and acetic acid ethyl ester. It is also possible to use mix- tures of the solvents mentioned.
  • Suitable acids and acidic catalysts are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminium trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid. Particular preference is given to sulfuric acid
  • the acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting mate- rials are generally reacted with one another in equimolar amounts.
  • Compounds Xl. b wherein the condensed ring is 1 H-[1 ,5]naphthyridin-2-one, can be prepared, from 2-halo-3-aminopyridines XII. a, wherein Hal is fluoride, chloride, bromide or iodide, especially fluoride or chloride, by reaction with acrylates (e.g. ethyl acrylate) as illustrated in Chem. Pharm. Bull. 1985, 33 (1 1), 4764 et sqq. and shown below.
  • the resulting compounds Xl. b may be further transformed to the corresponding chloride using POCb and reacted with various nucleophiles:
  • the first reaction is carried out at temperatures of from O 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of a palladium catalyst and a phosphine ligand, such as palladium(ll) acetate and tri-p-tolyl- phosphane.
  • the second (ring-closing) step may be carried out under basic conditions at temperatures of from 0 0 C to 200 0 C, preferably from 25°C to 200°C, preferably in an inert organic solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halo- genated hydrocarbons such as D
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide, alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethy
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Compounds Xl. c wherein the condensed ring is 6H-[1 ,6]naphthyridin-5-one, may be prepared, e.g., from 2-halo-3-cyanopyridines XII. b by reaction with ethyne as illustrated in Chem. Pharm. Bull. 1985, 33 (2), 626 et sqq. and shown below:
  • the first reaction is carried out at temperatures from 0 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of a palladium catalyst and a phosphine ligand, such as palladium(ll) acetate and tri-p-tolyl- phosphane.
  • the last (ring-closing) step may be carried out under basic conditions.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as dichloromethane (DCM), chloroform and chloroben- zene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • alcohols such as methanol, etha- nol, n-propanol, isopropanol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being possible to use mixtures of these solvents.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide, alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicar- bonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropyle
  • alkali metal alkoxides such as sodium and potassium methoxide
  • sodium and potassium ethoxide are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the first reaction is carried out at temperatures of from about -80 0 C to 25°C, preferably from about -80 0 C to 0 0 C, in an inert organic solvent in the presence of an organolithium base such as lithium diisopropylamide , n-butyl lithium, sec-butyl lith- ium or tert-butyl lithium.
  • organolithium base such as lithium diisopropylamide , n-butyl lithium, sec-butyl lith- ium or tert-butyl lithium.
  • the second (ring-closing) step is may be performed under acidic conditions at temperatures of from about 0°C to 200°C, preferably from 25°C to 200 0 C, in an inert organic solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halo- genated hydrocarbons such as D
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester,
  • Suitable acids and acidic catalysts for the ring-clsoing step are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminium trichloride, iron(lll) chlo- ride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, ben- zenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, ben- zenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • the bases and acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the reaction is carried out at temperatures from 0 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of a base or an acid.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being possible to use mixtures of these solvents.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide, alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal hydrides lithium hy- dride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, diiso
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable acids and acidic catalysts are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminium trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • the acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • compounds Xl. e can also be prepared, from 2-amino-3-methylamino- pyridines XII. e by reaction with 1 ,1 ,1-trialkoxyalkanes, wherein R' is Ci-Cio-alkyl, in the presence of an acid or base as illustrated in J. Org. Chem. 1964, 29(10), 2903 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XII. d with amidines.
  • Compounds XLf wherein the condensed ring is pyrido[2,3-b]pyrazine, can be prepared, for example, from 2,3-diaminopyridines Xl Lf by reaction with glyoxal or a suitable derivative of the latter in the presence of an acid or a base as illustrated in Can. J. Chem. 1988, 66 (6), 1500 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XILd with amidines.
  • Compounds XLg wherein the condensed ring is 1 H-pyrrolo[2,3-b]pyridine and R f is as defined above, preferably hydrogen or Ci-Cio-alkyl, can be prepared, for example, from 2-aminopyrroles XIII, wherein R f is as defined above, by reaction with 1 ,3-diketones, wherein R a is as defined above, preferably hydrogen or Ci-Cio-alkyl, in the presence of an acid or a base as illustrated in J. Chem. Soc. Perkin Trans. 1 1975, 19, 1920 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XILd with amidines.
  • Analogous routes may be employed to access to compounds Xl, wherein the condensed ring is furo[2,3-b]pyridine or thieno[2,3-b]pyridine.
  • Compounds XLh wherein the condensed ring is 1 H-pyrrolo[3,2-b]pyridine and R f is as defined above, preferably hydrogen or Ci-Cio-alkyl, can be prepared, for example, from 2-(2,2-dialkoxyethyl)-3-aminopyridines XILg, wherein R f is as defined above preferably hydrogen or Ci-Cio-alkyl, and R' is Ci-Cio-alkyl, in the presence of a base or an acid as illustrated in Chem. Pharm. Bull. 1986, 34 (6), 2362 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XILd with amidines.
  • Analogous routes may be employed to access to compounds Xl, wherein the condensed ring isfuro[3,2-b]pyridine or thieno[3,2-b]pyridine.
  • Compounds XLj, wherein the coondenes ring is 1 H-imidazo[4,5-b]pyridine can be prepared, for example, from 1 ,4-diamino imidazoles XIV by reaction with 1 ,3-diketones as illustrated in J. Het. Chem. 1983, 20 (4), 1015 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XII. d with amidines.
  • Analogous routes may be employed to access to compounds Xl, wherein the con- densed ring is 3H-imidazo[4,5-b]pyridine, thiazolo[4,5-b]pyridine, oxazolo[4,5-b]pyri- dine, thiazolo[5,4-b]pyridine or oxazolo[5,4-b]pyridine.
  • Compounds Xl. k wherein the condensed ring is 2,2-dimethyl-[1 ,3]dioxolo[4,5-b]py- ridine, can be prepared, for example, from 1 ,4-dihydro-pyridine-2,3-diones XV by reaction with acetone or 2,2-dimethoxy-propane as illustrated in J. Het. Chem. 1983, 20 (3), 703 et sqq. and Bioorg. Med. Chem. Lett. 2003, 13 (22), 4133 et sqq., respectively and shown below:
  • the reaction is carried out at temperatures of from 0 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of an acid.
  • suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being possible to use mixtures of these solvents.
  • Suitable acids and acidic catalysts are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminium trichloride, iron(lll) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • the acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Hal is fluoride, chloride, bromide or iodide, especially fluoride or chloride and PG is a suitable protection group such as benzyl, trimethylsilyl, triisopropylsilyl, tert- bytyldimethylsilyl, by reaction with a suitably protected 1 ,2-diol, wherein PG is a suitable protection group such as the ones described earlier, followed by deprotection and a ring-closing step as illustrated in Heterocycles 1994, 38 (6), 1355 et sqq. and shown below:
  • the first reaction is carried out at temperatures of from O 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of a base.
  • the ring-closing step may be performed under acidic or basic conditions.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halo- genated hydrocarbons such as D
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being possible to use mixtures of these solvents.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alka- line earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide, alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium ydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropy
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable acids and acidic catalysts are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as wie boron trifluoride, aluminium trichloride, iron(lll) chloride, tin(IV) chloride, tita- nium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • the acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Compounds Xl. n, wherein the condensed ring is 2,3-dihydro-furo[2,3-b]pyridine can be prepared, for example, from 3-(2-hydroxy-ethyl)-pyridin-2-ols Xll.j in the presence of an acid as illustrated in Heterocycles 1979, 12 (4), 493 et sqq. and shown below:
  • Analogous routes may be employed to access to compounds Xl, wherein the condensed ring is 2,3-dihydro-furo[3,2-b]pyridine, 3,4-dihydro-2H-pyrano[2,3-b]pyridine or 3,4-dihydro-2H-pyrano[3,2-b]pyridine.
  • Compounds Xl. n can also be prepared, for example, from 3-(2-halo-ethyl)-pyridyl-
  • the first reaction is carried out at temperatures of from 0 0 C to 200 0 C, preferably from 25°C to 200 0 C, in an inert organic solvent in the presence of a base.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halo- genated hydrocarbons such as DCM, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, MTBE, dioxane, anisole and THF, nitriles such as ace- tonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petrol ether
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halo- genated hydrocarbons such as D
  • alcohols such as methanol, ethanol, n-propanol, isopro- panol, n-butanol and tert.-butanol, and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being possible to use mixtures of these solvents.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide, alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal hydrides lithium hy- dride, sodium hydride, potassium ydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, di
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable acids and acidic catalysts are anorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as wie boron trifluoride, aluminium trichloride, iron(lll) chloride, tin(IV) chloride, tita- nium(IV) chloride and zinc(ll) chloride, moreover organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid.
  • the acids are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • compounds Xl. n for example, from 2-(2-halo-pyridin-3-yl)-ethanols XII. m, wherein Hal is fluoride, chloride, bromide or iodide, especially fluoride or chloride in the presence of a base as illustrated in J. Am. Soc. 1969, 91 (23), 6464 et sqq. and J. Het. Chem. 1987, 24 (3), 725 et sqq. and shown below:
  • This reaction can be conducted under similar conditions as described for reacting compounds XII. k to obtain compounds Xl. n. If individual compounds II, IV and IX cannot be obtained by the routes described above, they can be prepared by derivatization of compounds Xl.
  • Compounds IV wherein L' is methylsulfonyl or toluenesulfonyl, may be prepared under standard conditions by reacting the corresponding alcohol with methanesulfonic anhydride or trifluoromethanesulfonic anhydride, respectively, in analogy to methods described in J. Org. Chem. 50, 165-2170, 1985; or J. Chem. Soc. Perkin Trans. 1 : Org. Bioorg. Chem. 12, 2887-2894, 1980.
  • the group R may be present in compounds Il or may be introduced at a later stage as shown below by standard conditions in analogy to Coll. Czechoslovak. Chem. Comm. 40(4), 1 193-1198, 1975 or J. Med. Chem. 19(12), 1409-1416, 1991 , upon reac- tion of compounds I, wherein R is hydrogen, with suitable compounds XVI, wherein the R and the leaving group L are as defined above and which compounds XVI are known in the art:
  • the N-oxides may be prepared from the compounds I according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-1308, 1981) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ).
  • an organic peracid such as metachloroperbenzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(11 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-1308, 1981) or oxone (cf. J. Am
  • the oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography. If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during workup for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C ⁇ -alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g.
  • Ci-C4-haloalkyl refers to a straight-chained or branched alkyl group hav- ing 1 to 4 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms, e. g.
  • Ci-C ⁇ -haloalkyl refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms.
  • Ci-C ⁇ -alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. OCH 3 , OCH 2 CH 3 , O(CH 2 ) 2 CH 3 , 1-methylethoxy, O(CH 2 ) 3 CH 3 , 1-methyhpropoxy, 2-methylpropoxy or 1 ,1-dimethylethoxy, 0(CH 2 ⁇ CH 3 or O(CH 2 ) 5 CH 3 .
  • Ci-C4-alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • Ci-C4-haloalkoxy refers to a Ci-C4-alkoxy group, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, e.g. OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCCI 3 , chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro->ethoxy, OC 2 F 5 , 2-fluoropropoxy, 3-fluoropropoxy,
  • Ci-C ⁇ -haloalkoxy refers to a Ci-C6-alkoxy group, wherein some or all of the hydrogen atoms may be replaced by halogen atoms.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group.
  • Ci-Ce-alkoxy-Ci-C ⁇ -alkyl refers to alkyl having 1 to 6 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a d-C ⁇ -alkoxy group.
  • Ci-C4-haloalkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-haloalkoxy group.
  • Ci-C4-haloalkoxy-Ci-C ⁇ -alkyl refers to alkyl having 1 to 6 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a d-C ⁇ -alkoxy group.
  • Ci-Ce-alkoxy-Ci-C ⁇ -alkoxy refers to an Ci-C ⁇ -alkoxy-Ci-C ⁇ -alkyl group, which is bonded via an oxygen atom to the remainder of the molecule.
  • Ci-C4-alkylthio refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms bonded via a sulfur atom, at any position in the alkyl group, e. g. methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • d-C ⁇ -alkylthio refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms bonded via a sulfur atom.
  • Ci-C4-haloalkylthio and “d-C ⁇ -haloalkylthio” refer to straight-chain or branched haloalkyl groups having 1 to 4 or 1 to 6 carbon atoms bonded through a sulfur atom, at any position in the haloalkyl group.
  • Ci-C4-alkylamino refers to an amino radical carrying one Ci-C4-alkyl group as substituent, e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1-dimethylethylamino and the like.
  • d-C ⁇ -alkylamino refers to an amino radical carrying one d-C ⁇ -alkyl group as substituent.
  • di(Ci-C4-alkyl)amino refers to an amino radical carrying two identical or different Ci-C4-alkyl groups as substituents, e. g. dimethylamino, diethylamino, di-n- propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N-methylamino, and the like.
  • di(Ci-C6-alkyl)amino refers to an amino radical carrying two identical or different d-C ⁇ -alkyl groups as substituents.
  • d-C ⁇ -haloalkylamino and "di(Ci-C4-haloalkyl)amino", respectively, refer to amino radicals carrying one and two identical or different d-C ⁇ -alkyl groups as substituents, respectively.
  • Ci-C4-alkylcarbonyl refers to a d-C ⁇ -alkyl radical which is attached via a carbonyl group.
  • (Ci-C6-alkoxy)carbonyl refers to a d-C ⁇ -alkoxy radical which is attached via a carbonyl group.
  • d-C ⁇ -haloalkylcar- bonyl and “d-C ⁇ -haloalkoxycarbonyl”, respectively, refer to a d-C ⁇ -alkyl radical and a d-C ⁇ -alkoxy radical, respectively, which are attached via a carbonyl group.
  • Ci-C ⁇ -alkylaminocarbonyl refers to a d-C ⁇ -alkylamino radical which is attached via a carbonyl group.
  • di(d-C6-alkyl)aminocarbonyl refers to a di(Ci-C6)alkylamino radical which is attached via a carbonyl group.
  • phenoxy and refers to a phenyl radical which is attached via an oxygen atom.
  • phenoxy-Ci-C ⁇ -alkyl and refers to a phenoxy radical which is attached via a d-C ⁇ -alkyl group.
  • C2-C4-alkenyl refers to a straight-chain or branched unsaturated hydro- carbon radical having 2 to 4 carbon atoms and a double bond in any position, e.g. ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • C2-C4-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.
  • Cs-Cs-cycloalkyl refers to monocyclic, bicyclic and bridged saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or norbornyl.
  • Ci-C6-alkyl-C3-C8-cycloalkyl refers to a cycloalkyl radical having 3 to 8 carbon atoms (as defined above), wherein one hydrogen atom of the cycloalkyl radical is replaced by a d-C ⁇ -alkyl group.
  • 5-, 6- or 7-membered carbocycle is to be understood as meaning both saturated or partially unsaturated carbocycles having 5, 6 or 7 ring members as well as phenyl.
  • non-aromatic rings include cyclopentyl, cyclopentenyl, cyclopen- tadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cyclo- heptadienyl, and the like.
  • the term "5-, 6-, or 7-membered heterocycle" wherein the ring member atoms of the heterocycle include besides carbon atoms one, two, three or four heteroatoms selected from the group of N, O and S, is to be understood as meaning both saturated and partially unsaturated as well as aromatic heterocycles having 5, 6 or 7 ring atoms.
  • Examples include: saturated and partially unsaturated 5-, 6-, or 7-membered heterocycle wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2 or 3 heteroatoms selected from the group of N, O and S, and which is saturated or partially unsaturated, e. g.
  • heteroarenediyl refers to a divalent radical derived from an aromatic heteroaryl having two points of attachment. Examples of heteroarenediyl radicals are, e.g.
  • the aforementioned groups can be C-attached or N-attached where such is possible; e. g. a group derived from pyrrole, imidiazole or pyrazole can be N-attached or C-attached.
  • phenylene refers to 1 ,2-phenylene (o-phenylene), 1 ,3-phenylene (m-phenylene) and 1 ,4-phenylene (p-phenylene).
  • two radicals R b that are bound to adjacent ring member atoms of the group A may form together with said ring member atoms a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic cycle” refers to a condensed bicyclic ring system, wherein the 5- or 6-membered heteroarenediyl and phenylene, respectively carry a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring.
  • fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic aromatic cycle which may be a car- bocycle or heterocycle
  • fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic aromatic cycle which may be a car- bocycle or heterocycle
  • fused-on 5- or 6-membered partially unsaturated or aromatic heterocycle refers to a 5- or 6-membered partially unsaturated or aromatic heterocycle that is part of a condensed bicyclic ring system.
  • the pyridyl ring carries a fused-on 5- or 6-membered partially unsaturated or aromatic heterocyclic ring bound to the adjacent ring member atoms in position 2 and 3.
  • the term "condensed ring” refers to the overall condensed bicyclic ring system comprising the pyridyl ring and the fused-on 5- or 6-membered partially unsaturated or aromatic heterocycle.
  • Agriculturally acceptable salts of compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfo- nium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the compounds of formula I can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention. Depending on the substitution pattern, the compounds of formula I and their
  • N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.
  • the embodiments of the intermediates correspond to the embodiments of the compounds I.
  • One embodiment of the invention relates to compounds I, wherein n is 1 or 2.
  • An- other embodiment relates to compounds I, wherein n is 2.
  • a further embodiment relates to compounds I, wherein n is 1.
  • a further embodiment relates to compounds I, wherein n is 0.
  • R a is halogen, CN, NH 2 , d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, d-C ⁇ -haloalkylthio, d-C ⁇ -alkylamino, d-C ⁇ -haloalkylamino, di(d-C6-alkyl)amino, di(d-C6-haloalkyl)amino, Ci-C ⁇ -alkyl- carbonyl, d-C ⁇ -haloalkylcarbonyl, Ci-C6-alkoxycarbonyl, d-C ⁇ -haloalkoxycarbonyl, Ci-d-alkoxy-Ci-d-alkyl, d-C ⁇ -alkylaminocarbonyl, di(d-C6-alkyl)aminocarbonyl.
  • R a is halogen, CN, d-d-alkyl, Ci-C4-haloalkyl, Ci-d-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, C 3 -C8-cycloalkyl or d-d-alkyl-Cs-Cs-cycloalkyl.
  • R a is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, d-d-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio or di(Ci-C4-alkyl)amino.
  • R a is CH 2 CH 3 , CH 2 (CHs) 2 , CF 3 , OCH 3 , OCH 2 CH 3 , isopro- poxy, OCF 3 , OCHF 2 , NHCH 3 , N(CHs) 2 , NHCH 2 CH 3 or NHCH 2 (CHs) 2 .
  • R a is CH 2 CH 3 , CH 2 (CHs) 2 , CF 3 , OCH 2 CH 3 , isopropoxy, OCF 3 , OCHF 2 , N(CHs) 2 , NHCH 2 CH 3 or NHCH 2 (CHs) 2 .
  • R a is halogen and preferably selected from F and Cl and in particular, R a is Cl.
  • R a is CN.
  • R a is Ci-C ⁇ -alkyl and preferably selected from methyl, ethyl, n-propyl, i-propyl and t-butyl.
  • R a is d-C ⁇ -haloalkyl. More preferably, R a is d-haloalkyl and selected from fluormethyl, difluormethyl, trifluormethyl, chlormethyl, dichlormethyl and trichlormethyl, and in particular, R a is trifluormethyl.
  • R a is Ci-d-alkoxy and preferably selected from methoxy, ethoxy, n-propyloxy and i-propyl- oxy.
  • One embodiment relates to compounds I, wherein the Het is a 5-membered partially unsaturated or aromatic heterocycle, more preferably a partially unsaturated heterocy- cle.
  • a further embodiment relates to compounds I, wherein Het is a 5- or 6-membered partially unsaturated heterocycle, more preferably a 6-membered partially unsaturated heterocycle.
  • a further embodiment relates to compounds I, wherein Het is a 5- or 6-membered heteroaryl, more preferably a 5-membered heteroaryl.
  • a further embodiment relates to compounds I, wherein Het is a 5-membered het- erocycle, preferably selected from the group consisting of dihydrofuran, furan, pyrrole, thiophene, pyrazole, isoxazole, isothiazole, imidazole, oxazole and thiazole.
  • Het is a 5-membered het- erocycle, preferably selected from the group consisting of dihydrofuran, furan, pyrrole, thiophene, pyrazole, isoxazole, isothiazole, imidazole, oxazole and thiazole.
  • a further embodiment relates to compounds I, wherein Het is a 6-membered heterocycle, and preferably selected from the group consisting of pyrane, pyridine, pyrimidine, pyrazine and pyridazine.
  • Het is selected from the respective column of table P.
  • R a1 and R a2 are each inde- pendently hydrogen or have one of the definitions specified for R a and wherein the pyridyl group carries one of the following combinations of the fused-on ring, R a1 and R a2 as defined in Table P, which compounds are of formula 1.1
  • R is hydrogen, C-i-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, C-i-C ⁇ -alkylcarbonyl or C-i-C ⁇ -haloalkylcarbonyl, preferably hydrogen or d-Ce-alkyl.
  • R is hydrogen, Ci-C 4 -alkyl, Ci-C2-haloalkoxy, di(Ci-C2-alkyl)amino, allyl or propargyl.
  • a further embodiment relates to compounds I, wherein R is Ci-C 4 -alkyl and preferably selected from methyl, ethyl, n-propyl and i-propyl, and in particular, R is methyl.
  • a further embodiment relates to compounds I, wherein R is hydrogen and wherein R a1 , R a2 and R a3 are each independently hydrogen or have one of the definitions specified for R a , especially those being preferred, which compounds are of formula 1.2
  • One embodiment relates to compounds I, wherein A is phenylene, which ist unsub- stituted or carries one, two, three or four identical or different substituents R b , with 1 ,3-phenylene or 1 ,4-phenylene being preferred.
  • Another embodiment relates to compounds I, wherein A is 1 ,4-phenylene, which is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R b , in particular A is 1 ,4-phenylene, which is unsubstituted.
  • a further embodiment relates to compounds I, wherein A is phenylene or a 5- or 6- membered heteroarenediyl, wherein the ring member atoms of the heteroarenediyl include besides carbon atoms 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the aforementioned divalent radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different groups R b .
  • a further embodiment relates to compounds I, wherein A is a heteroarenediyl se- lected from the group consisting of pyrimidindiyl, pyridazindiyl, pyrazindiyl, triazindiyl, furandiyl, pyrroldiyl, pyrazoldiyl, isoxazoldiyl, isothiazoldiyl, imidazoldiyl, oxazoldiyl, thiazoldiyl, triazoldiyl, thiadiazoldiyl and oxadiazoldiyl, and wherein the aforementioned radicals are unsubstituted or carry 1 , 2 or 3 identical or different substituents R b .
  • A is pyrimidindiyl.
  • A is pyridazindiyl.
  • A is pyrazindiyl.
  • A is furandiyl.
  • A is pyrroldiyl.
  • A is pyrazoldiyl.
  • A is isoxa- zoldiyl.
  • A is isothiazoldiyl. In a further embodiment, A is imidazoldiyl. In a further embodiment, A is oxazoldiyl. In a further embodiment, A is thiazoldiyl. In a further embodiment, A is 1 ,2,4-triazoldiyl. In a further embodiment, A is 1 ,2,4-thiadiazoldiyl. In a further embodiment, A is 1 ,2,4-oxadiazoldiyl.
  • a further embodiment relates to compounds I, wherein A is a 6-membered het- eroarenediyl, which is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R b .
  • a further embodiment relates to compounds I, wherein A is a heteroarenediyl selected from the group consisting of pyrimidindiyl, pyridazindiyl, pyrazindiyl, furandiyl, thiendiyl and pyrazoldiyl, and more preferably selected from the group consisting of pyrimidindiyl, pyridazindiyl and pyrazindiyl, and wherein the aforementioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R b .
  • a further embodiment relates to compounds I, wherein A is thiendiyl.
  • A is a 6-membered heteroarenediyl
  • A is pyrimidinyl
  • each of the aforementioned two radicals are unsubstituted or carry 1 , 2 or 3 identical or different substituents R b
  • A is selected from the group consisting of pyrimidin-2,5-diyl, pyrimidin-2,4-diyl and pyrimidin-4,6-diyl wherein the aforementioned heteroarenediyl radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R b .
  • a further embodiment relates to compounds I, wherein A is a 5-membered heteroarenediyl, which is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R b .
  • Particularly preferred embodiments of the invention relate to compounds I, in which A is one of the following radicals A-1 to A-5:
  • # indicates the bond to the sulfur atom of the suforifcSnide group; and * indicates the bond to Y.
  • One embodiment of the invention relates to compounds I, wherein the group A carries 1 , 2 or 3 radicals R b , more preferably 1 or 2 radicals R b .
  • the group A is unsubstituted or carries 1 radical R b .
  • the group A is unsubstituted.
  • the group A carries 1 radical R b .
  • the group A carries 2 radicals R b .
  • the group A carries 3 radicals R b .
  • R b is preferably halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkylaminocarbonyl or di(Ci-C4-alkyl)aminocarbonyl.
  • R b is halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-halo- alkoxy.
  • R b is halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl or Ci-C4-alkoxy.
  • R b is halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl or Ci-C2-alkoxy.
  • a further embodiment relates to compounds I, wherein R b is F, Cl, CN, Ci-C2-alkyl, Ci-C2-haloalkyl or Ci-C2-alkoxy.
  • a further embodiment relates to compounds I, wherein R b is F, Cl, CN, CH3, OCH3, CF3 or OCHF2.
  • a further embodiment relates to compounds I, wherein R b is F or CH 3 .
  • R b is halogen and preferably selected from fluorine and chlorine, and in particular, chlorine.
  • R b is CN.
  • R b is Ci-C4-alkyl and preferably selected from methyl, ethyl, n-propyl and i-propyl, and in particular, methyl.
  • R b is Ci-C4-haloalkyl. More preferably, R b is Ci-haloalkyl, and in particular, trifluoromethyl.
  • R b is Ci-C4-alkoxy and preferably selected from methoxy and ethoxy.
  • two radicals R b that are bound to adjacent ring member atoms of the group A do not form together with said ring member atoms any fused cycle.
  • a further embodiment relates to compounds I, wherein two radicals R b that are bound to adjacent ring member atoms of the group A form together with said ring member atoms a fused cycle being a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused cycle is unsubstituted and carries 1 , 2, 3 or 4 identical or different groups as defined for R b .
  • the fused cycle is preferably phenyl.
  • the fused cycle is preferably a saturated carbocycle and in particular cyclohexyl.
  • the fused cycle is preferably a partially unsaturated carbocycle and in particular cyclohexenyl.
  • One embodiment of the invention relates to compounds I, wherein p is 1 , 2 or 3, preferably 1 or 2, in particular 1.
  • a further embodiment relates to compounds I, wherein p is 2.
  • a further embodiment relates to compounds I, wherein p is 3.
  • a further embodiment relates to compounds I, wherein p is 0.
  • two radicals R c that are bound to adjacent ring member atoms of the phenyl ring do not form together with said ring member atoms any fused cycle.
  • R c is halogen and preferably selected from F and Cl and in particular, R c is Cl.
  • R c is CN.
  • R c is Ci-C ⁇ -alkyl and preferably selected from methyl, ethyl, n-propyl and i-propyl, and in particular, R c is methyl.
  • R c is Ci-C6-haloalkyl. More preferably, R c is Ci-haloalkyl and selected from fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and trichloromethyl, and in particular, R c is trifluoromethyl.
  • R c is Ci-C ⁇ -alkoxy and preferbly selected from methoxy and ethoxy.
  • R c is Cs-Cs-cycloalkyl and preferably selected from cyclopropyl, cylopentyl and cyclohexyl, and in particular, R c is cyclopropyl.
  • R c is Ci-C ⁇ -alkyl-Cs-Cs-cycloalkyl and selected from cylopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl and cyclo- octylmethyl.
  • R c is phenyl. In a further embodiment, R c is phenoxy. In a further embodiment, R c is phenoxy-d-C ⁇ -alkyl and selected from phenoxymethyl, 1 -phenoxy-ethyl and 2-phenoxyethyl.
  • R c is a 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein R c is unsubstituted or carries 1 , 2, 3 or 4 identical or different groups R d .
  • R c is a 5-membered heteroaryl
  • R c carries 1 heteroatom as ring member atom.
  • R c is a furanyl radical that is unsubstituted or carries 1 , 2 or 3 identical or different substituents R d .
  • R c is a thienyl radical that is unsubstituted or carries 1 , 2 or 3 identical or different substituents R d .
  • R c is a pyrrolyl radical selected from pyrrol-2-yl and pyrrol-3-yl, wherein the aforementioned pyrrolyl radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R d .
  • R c is a 5-membered heteroaryl
  • R c carries 2 heteroatoms as ring member atoms.
  • R c is a pyrazolyl radical selected from pyrazol-3-yl, pyrazol- 4-yl and pyrazol-5-yl, wherein the aforementioned pyrazolyl radicals are unsubstituted or carry 1 , 2 or 3 identical or different substituents R d .
  • R c is an isoxazolyl radical that is unsubstituted or carries 1 or 2 identical or different substituents R d .
  • R c is an isothiazolyl radical that is unsubstituted or carries 1 or 2 identical or different substituents R d .
  • R c is an imidazolyl radical that is unsubstituted or carries 1 , 2 or 3 identical or different substituents R d .
  • R c is an oxazolyl radical that is unsubstituted or carries 1 or 2 identical or different substituents R d .
  • R c is a thiazolyl radical that is unsubstituted or carries 1 or 2 identical or different substituents R d .
  • a further embodiment relates to compounds I, wherein two radicals R c that are bound to adjacent ring member atoms of the phenyl ring form together with said ring member atoms a fused cycle being a fused 5-, 6- or 7-membered saturated, partially unsaturated or aromatic carbocycle or heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the fused cycle is unsubstituted and carries 1 , 2, 3 or 4 identical or different R e radicals.
  • the fused cycle is preferably phenyl.
  • R' is Ci-haloalkyl and selected from fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl and trichloromethyl.
  • R' is preferably Ci-C 4 -haloalkoxy and preferably halomethoxy, such as di- fluoromethoxy, trifluoromethoxy, dichloromethoxy and trichloromethoxy, or haloethoxy, such as 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2-dichloroethoxy and 2,2,2-trichloro- ethoxy.
  • R' is preferably di(Ci-C4-alkyl)amino and more preferably selected from dimethylamino, methyl-ethyl-amino, methyl-n-propyl-amino, methyl-i-propyl-amino, methyl-n-butyl-amino, methyl-(1-methyl-propyl)-amino, methyl- (2-methylpropyl)-amino, methyl-(1 ,1-dimethylethyl)-amino, diethylamino, and in particular from dimethylamino, methyl-ethylamino and diethylamino.
  • R" is preferably Ci-C 4 -alkyl and more preferably selected from methyl, ethyl, n-propyl, i-propyl, and in particular, R" is methyl.
  • R" is preferably C2-C 4 -alkenyl and selected from vinyl, prop-1-en-3-yl, but-1-en-3-yl, but- 1-en-4-yl and but-2-en-1-yl.
  • R" is preferably C 2 -C 4 -alkynyl and selected from prop-1-in-3-yl, but-1-in-3-yl, but-1-in-4-yl and but-2-in-1-yl.
  • R" is preferably Ci-C 4 -alkoxy-Ci-C 4 -alkyl and more preferably selected from methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl.
  • R c relates to compounds I, wherein R c carries 1 , 2, 3 or 4 radicals R d , preferably 1 , 2 or 3 radicals R d , and more preferably 1 or 2 radicals R d .
  • R c carries one radical R d .
  • R c carries two radicals R d .
  • the group R c carries three radicals R d .
  • R d is halogen and preferably selected from F and Cl, and in particular, Cl.
  • R d is CN.
  • R d is Ci-C 4 -alkyl and preferably selected from methyl, ethyl, n-propyl and i-propyl and in particular, R d is methyl.
  • R d is Ci-C 4 -haloalkyl. More preferably, R c is C-i-haloalkyl and selected from fluoromethyl, difluoromethyl, trifluoromethyl, chloro- methyl, dichloromethyl and trichloromethyl, and in particular, R d is trifluoromethyl.
  • R d is Ci-C 4 -alkoxy and preferably selected from methoxy and eth- oxy.
  • R d is Ci-C 4 -haloalkoxy and preferably halomethoxy such as difluoromethoxy, trifluoromethoxy, dichloromethoxy and trichloromethoxy; or halo- ethoxy such as 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2-dichloroethoxy and 2,2,2-trichloroethoxy.
  • Particularly preferred embodiments of the invention relate to compounds I, wherein the phenyl group carries one of the following combinations of R c1 , R c2 , R c3 , R c4 and R c5 as defined in Table A:
  • a further embodiment relates to compounds I, wherein R is hydrogen and wherein R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , especially those being preferred, which compounds are of formula 1.3
  • One embodiment relates to compounds I, wherein Y is a direct bond, -O-, -S- or -NH-. Another embodiment relates to compounds I, wherein Y is -S- or -O-. A further embodiment relates to compounds I, wherein R is hydrogen, and Y is -O-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • a further embodiment relates to compounds I, wherein R is hydrogen and Y is a di- rect bond, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • R is hydrogen and Y is a di- rect bond
  • R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a
  • R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • a further embodiment relates to compounds I, wherein Y is -N(R ⁇ )-, wherein R ⁇ is hydrogen or Ci-C4-alkyl. If R ⁇ is present, in one embodiment of the invention, R ⁇ is Ci-C4-alkyl, and preferably selected from methyl, ethyl, n-propyl and i-propyl, and in particular, R ⁇ is methyl.
  • R is hydrogen and Y is -N(CHs)-
  • R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a
  • R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.C:
  • a further embodiment relates to compounds I, wherein R is hydrogen and Y is -NH-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I. D:
  • a further embodiment relates to compounds I, wherein R is hydrogen and Y is -S-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • R is hydrogen and Y is -S-
  • R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a
  • R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a
  • R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a
  • R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the defi ted by formula I.
  • a further embodiment relates to compounds I, wherein Y is is -CH2-.
  • a more specific embodiment relates to compounds I, wherein R is hydrogen, Y is -CH2-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified fo I.
  • H
  • a further embodiment relates to compounds I, wherein R is hydrogen and Y is -O(CH2)-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula IJ:
  • a further embodiment relates to compounds I, wherein R is hydrogen and Y is -(CH2)O-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • K is hydrogen and Y is -(CH2)O-, and R a1 and R a2 are each independently hydrogen or have one of the definitions specified for R a , and R c1 , R c2 , R c3 , R c4 and R c5 are each independently hydrogen or have one of the definitions specified for R c , which are represented by formula I.
  • Table 3 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-3, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 4 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-4, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 5 Compounds of formula I.
  • A wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-7, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 8 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-8, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 9 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-9, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 10 Compounds of formula I.
  • Table 12 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-12, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 13 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-13, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 14 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-14, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 15 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-15, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 16 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-16, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 17 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-17, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 18 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-18, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 19 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-19, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 20 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-20, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 21 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-21 , A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 22 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-22, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 23 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-23, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 24 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-24, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 25 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-25, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 26 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-26, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 27 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-27, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 28 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-28, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 29 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-29, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 30 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-30, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 31 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-31 , A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 32 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-32, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 33 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-33, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Table 34 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in line P-34, A is A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 35 to 68 Compounds of formula I .A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in Tables 1 to 34 and A is A-2 instead of A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 69 to 102 Compounds of formula I.
  • Tables 137 to 170 Compounds of formula I. A, wherein the condensed ring system comprising Het, R a1 and R a2 is defined as in Tables 1 to 34 and A is A-5 instead of A-1 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 171 to 340 Compounds of formula I. B, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 341 to 510 Compounds of formula I. C, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 511 to 680 Compounds of formula I. D, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 681 to 850 Compounds of formula I. E, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 851 to 1020 Compounds of formula I. F, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 1021 to 1190 Compounds of formula I. G, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 1 191 to 1360 Compounds of formula I. H, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 1361 to 1530 Compounds of formula IJ, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • Tables 1531 to 1700 Compounds of formula I. K, wherein the condensed ring system comprising Het, R a1 and R a2 and A are defined as in Tables 1 to 170 and the meaning of R c1 , R c2 , R c3 , R c4 and R c5 for each compound corresponds to one line of table A.
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deu- teromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • plants g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
  • compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant.
  • cultivación of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultivated plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases: Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B.
  • Alternaria spp. Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternat
  • sorokiniana on cereals and e.g. B. oryzae on rice and turfs
  • Blumeria originally Erysiphe
  • graminis prowdery mildew
  • cereals e. g. on wheat or barley
  • Botrytis cinerea teleomorph: Botryotinia fuckeliana: grey mold
  • fruits and berries e. g. strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Drechslera syn. Helminthosporium, teleomorph: Pyrenophora
  • Moni- linia spp. e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e.
  • viticola (grapevine downy mildew) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P.
  • Puccinia spp. rusts
  • P. triticina brown or leaf rust
  • P. striiformis stripe or yellow rust
  • P. hordei dwarf rust
  • P. graminis seed or black rust
  • Erysiphe necator prowdery mildew, anamorph: Oidium tuckeri
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears.
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • the term "protection of materials” is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • the compounds I and compositions thereof may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • the invention also relates to agrochemical compositions comprising a solvent or solid carrier and at least one compound I and to the use for controlling harmful fungi.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • effective amount denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • the compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, OD, FS), emulsifiable con- centrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water- soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
  • composition types e. g. SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF
  • composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
  • compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J.
  • the agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions.
  • auxiliaries depend on the particular application form and active substance, respectively.
  • auxiliaries are solvents, solid carriers, dispersants or emulsi- fiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
  • Powders, materials for spreading and dusts can be prepared by mixing or conco- mitantly grinding the compounds I and, if appropriate, further active substances, with at least one solid carrier.
  • Granules e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • the agrochemical compositions generally comprise between 0.01 and 95%, pref- erably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • the compositions in question give, after two-to-tenfold dilu- tion, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations.
  • a suspension-type (FS) composition is used for seed treatment.
  • a FS composition may comprise 1-800 g/l of active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
  • the active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • active substances e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • carpropamid carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthio- farm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
  • C) azoles carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthio- farm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
  • - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)-cycloheptanol;
  • D) heterocyclic compounds pyridines fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di-carbo- nitrile, N-(1-(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro-nicotinamide;
  • - pyrimidines bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil;
  • - morpholines aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph; - piperidines: fenpropidin;
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin; non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhili- none, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole- 1-carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methyl- sulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quin-
  • - thio- and dithiocarbamates ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamo- carb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • guanidine guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
  • antibiotics kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, poly- oxine, validamycin A;
  • - nitrophenyl derivates binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fen- tin hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
  • organochlorine compounds chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quinto- zene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide;
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to I) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to F), as described above, and if desired one suitable solvent or solid carrier.
  • agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to I) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to F), as described above, and if desired one suitable solvent or solid carrier.
  • fungicide e. g. one or more fungicide from the groups A) to F
  • the weight ratio of component 1 and component 2 generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20: 1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :3 to 3:1.
  • the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1
  • the weight ratio of component 1 and component 3 preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1.
  • mixtures comprising a compound I (component 1 ) and at least one active substance selected from the strobilurines of group A) (component 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim- methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.
  • mixtures comprising a compound I (component 1 ) and at least one active substance selected from the carboxamides of group B) (component 2) and particularly selected from bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid and N-(3',4',5'-trifluorobiphenyl-2-yl)-3-di- fluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide.
  • mixtures comprising a compound of formula I (component 1 ) and at least one active substance selected from the azoles of group C) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquin- conazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.
  • mixtures comprising a compound I (component 1 ) and at least one active substance selected from the heterocyclic compounds of group D) (component 2) and particularly selected from fluazinam, cyprodinil, fenarimol, me- panipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquina- zid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine.
  • active substance selected from the heterocyclic compounds of group D) (component 2) and particularly selected from fluazinam, cyprodinil,
  • mixtures comprising a compound I (component 1 ) and at least one active substance selected from the carbamates of group E) (component 2) and particularly selected from mancozeb, metiram, propineb, thiram, iprovalicarb, ben- thiavalicarb and propamocarb.
  • mixtures comprising a compound I (component 1 ) and at least one active substance selected from the fungicides given in group F) (component 2) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat- methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine.
  • component 2 The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci.
  • the mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I. Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
  • the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I.
  • Example 1 Preparation of 4'-fluoro-biphenyl-4-sulfonic acid (2-dimethylamino- oxazolo[4,5-b]pyridin-7-ylmethyl)-amide a) Preparation of dimethyl-oxazolo[4,5-b]pyridin-2-yl-amine
  • HPLC column RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50 mm x 4,6 mm; Eluent: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % TFA (gradient from 5:95 to 95:5 in 5 min at 40 0 C, flow of 1 ,8 ml/min).
  • MS Quad- rupol Elektrospray lonisation, 80 V (positive mode).
  • the active substances were formulated separately as a stock solution in DMSO at a concentration of 10 000 ppm.
  • the stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using water.
  • An zoospore suspension of Phytophthora infestans in a pea juice-based aqueous nutrient medium for fungi was then added.
  • the plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of Pyricularia oryzae in a malt-based aqueous medium solution was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C.
  • the MTPs were measured at 405 nm 7 days after the inoculation.
  • the spray solutions were prepared in several steps:
  • the stock solution were prepared: a mixture of acetone and/or DMSO and the wet- ting agent/emulsifier Wettol EM 31 , which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 10 ml. Water was then added to total volume of 100 ml. This stock solution was diluted with the described solvent-em ulsifier-water mixture to the given concentration.
  • Young seedlings of tomato plants were grown in pots. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 20 0 C and a relative humidity close to 100% the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Leaves of pot-grown soy bean seedlings were inoculated with spores of Phakopsora pachyrhizi .
  • the plants were transferred to a humid chamber with a relative humidity of about 95% and 23 to 27°C for 24 h. The next day the plants were cultivated for 2 days in a greenhouse chamber at 23 to 27°C and a relative humidity between 60 and 80%. Then the plants were sprayed to run-off with the prepared stock solutions. The plants were allowed to air-dry. Then the trial plants were cultivated again for 12 days in a greenhouse chamber at 23- 27oC and a relative humidity between 60 and 80%. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pretreatment Of Seeds And Plants (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

La présente invention porte sur des pyridin-4-yl-méthyl sulfonamides de formule I, dans laquelle Het, Ra, Rc, Rf, m, n, p, R, A et Y sont tels que définis dans les revendications, sur les N-oxydes et sels de ceux-ci et sur leur utilisation pour combattre des champignons nuisibles, ainsi que sur des compositions et des semences comprenant au moins un tel composé. L'invention porte également sur un procédé et sur des intermédiaires de préparation de ces composés.
PCT/EP2009/056125 2008-05-28 2009-05-20 Pyridin-4-yl-méthyl sulfonamides substitués en tant que fongicides WO2009144159A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US12/994,572 US20110077154A1 (en) 2008-05-28 2009-05-20 Substituted pyridin-4-yl-methyl sulfonamides as fungicides
BRPI0912109-9A BRPI0912109A2 (pt) 2008-05-28 2009-05-20 Composto, processo para preparar os mesmos, composições agroquímicas, método para combater fungos nocivos fitopatogênicos, uso dos compostos, e, semente
JP2011510950A JP2011521924A (ja) 2008-05-28 2009-05-20 殺菌剤としての置換ピリジン−４−イル−メチルスルホンアミド
EP09753814A EP2300471A1 (fr) 2008-05-28 2009-05-20 Pyridin-4-yl-méthyl sulfonamides substitués en tant que fongicides
CN2009801196435A CN102046623A (zh) 2008-05-28 2009-05-20 作为杀真菌剂的取代的吡啶-4-基甲基磺酰胺

Applications Claiming Priority (4)

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EP08157079.8 2008-05-28
EP08157079 2008-05-28
EP09156946 2009-03-31
EP09156946.7 2009-03-31

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WO2009144159A1 true WO2009144159A1 (fr) 2009-12-03

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US (1) US20110077154A1 (fr)
EP (1) EP2300471A1 (fr)
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CN (1) CN102046623A (fr)
BR (1) BRPI0912109A2 (fr)
WO (1) WO2009144159A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8772293B2 (en) 2010-07-09 2014-07-08 Pfizer Limited Chemical compounds
US11827610B2 (en) 2021-09-15 2023-11-28 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006097489A1 (fr) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Biphenyl-n-(4-pyridyl)methylsulfonamides
WO2007002433A1 (fr) * 2005-06-22 2007-01-04 Plexxikon, Inc. Derives de pyrrolo [2, 3-b] pyridine utilises comme inhibiteurs de proteines kinases
WO2007093599A1 (fr) * 2006-02-14 2007-08-23 Basf Se Composes pyridin-4-ylmethylamide destines a lutter contre les organismes nuisibles
WO2008022937A1 (fr) * 2006-08-22 2008-02-28 Basf Se Picolyl amides d'acide thiophène-sulfonique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006097489A1 (fr) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Biphenyl-n-(4-pyridyl)methylsulfonamides
WO2007002433A1 (fr) * 2005-06-22 2007-01-04 Plexxikon, Inc. Derives de pyrrolo [2, 3-b] pyridine utilises comme inhibiteurs de proteines kinases
WO2007093599A1 (fr) * 2006-02-14 2007-08-23 Basf Se Composes pyridin-4-ylmethylamide destines a lutter contre les organismes nuisibles
WO2008022937A1 (fr) * 2006-08-22 2008-02-28 Basf Se Picolyl amides d'acide thiophène-sulfonique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8772293B2 (en) 2010-07-09 2014-07-08 Pfizer Limited Chemical compounds
US11827610B2 (en) 2021-09-15 2023-11-28 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

Also Published As

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CN102046623A (zh) 2011-05-04
US20110077154A1 (en) 2011-03-31
EP2300471A1 (fr) 2011-03-30
JP2011521924A (ja) 2011-07-28
BRPI0912109A2 (pt) 2015-07-28

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